CN115594405A - Low-dielectric high-temperature-stability LTCC material and preparation method thereof - Google Patents
Low-dielectric high-temperature-stability LTCC material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 239000000843 powder Substances 0.000 claims abstract description 72
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- 238000000498 ball milling Methods 0.000 claims abstract description 24
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- 239000002241 glass-ceramic Substances 0.000 claims abstract description 12
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- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 11
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- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 238000000748 compression moulding Methods 0.000 claims description 5
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 2
- 239000011365 complex material Substances 0.000 claims description 2
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
Abstract
The invention discloses a low dielectric and high temperature stability LTCC material which adopts a glass ceramic complex system material and comprises a part of microcrystalline glass and b part of Al 2 O 3 Ceramic powder, c parts of SiO 2 Ceramic powder, d parts of CaTiO 3 Ceramic powder and e parts of modifier; 55-60% of a, 20-25% of b, 10-15% of c, 8-12% of d, 1-3% of e, and =100% of a + b + c + d + e; the preparation method comprises the following steps: 1) Taking the ingredients; 2) Performing ball milling on the ingredients, uniformly mixing, and drying; 3) Adding adhesive, granulating, pressing, and sintering at 880-895 deg.C in air atmosphere. The invention adopts the microcrystalline glass and Al with specific contents 2 O 3 Ceramic powder, siO 2 Ceramic powder and CaTiO 3 The ceramic powder is compounded, and the prepared LTCC material can realize compact sintering below 900 ℃ and has a frequency temperature coefficient close to zero.
Description
Technical Field
The invention relates to the technical field of functional ceramic materials, in particular to a low-dielectric high-temperature-stability LTCC material and a preparation method thereof.
Background
The Low Temperature Co-fired Ceramic (LTCC) technology is a novel multilayer substrate technology developed in the middle of the last 80 th century, the sintering Temperature is generally below 900 ℃, and the LTCC technology can be Co-fired with Ag.
The main performance indexes of the LTCC material are dielectric constant, quality factor and frequency temperature coefficient. With the advent of the 5G era, LTCC materials are generally required to: low dielectric constant, high quality factor (low dielectric loss), near zero temperature coefficient of frequency. In the low-dielectric LTCC material, caO-MgO-SiO 2 Is microcrystalline glass and Al 2 O 3 The glass ceramic system LTCC material prepared by ceramic compounding has excellent performance, for example, the invention patent CN 109721340A discloses a high-strength low-loss LTCC material and a preparation method thereof, caO-MgO-SiO is used 2 Is microcrystalline glass and Al 2 O 3 The LTCC material with dielectric constant of about 6.5-8.5, dielectric loss less than 1.2 thousandth and bending strength greater than 200MPa is obtained by compounding the ceramics. However, the frequency temperature coefficient of the material is relatively large, and is generally-40 to-50 ppm/DEG C. The frequency temperature coefficient is the change degree of the material performance along with the temperature change, and the closer the numerical value is to zero, the smaller the influence of the temperature on the performance is, and the more stable the manufactured device is. Therefore, caO-MgO-SiO is used in places with high requirements on the stability of devices 2 Is microcrystalline glass and Al 2 O 3 Ceramic composite applications can be limited.
It is to be noted that the information disclosed in the above background section is only for understanding the background of the present application and thus may include information that does not constitute prior art known to a person of ordinary skill in the art.
Disclosure of Invention
In order to solve the problem that the LTCC material in the prior art has a large frequency temperature coefficient, the invention mainly aims to provide the LTCC material with low dielectric and high temperature stability.
The invention further aims to provide a preparation method of the LTCC material with low dielectric constant and high temperature stability.
The technical problem of the invention is solved by the following technical scheme:
the invention discloses a low-dielectric high-temperature-stability LTCC material which adopts a glass ceramic complex material and comprises a part of microcrystalline glass and b part of Al in percentage by mass 2 O 3 Ceramic powder, c part of SiO 2 Ceramic powder, d parts of CaTiO 3 Ceramic powder and e parts of modifier; wherein a is 55-60%, b is 20-25%, c is 10-15%, d is 8-12%, e is 1-3%, and a + b + c + d + e =100%.
In some embodiments, the microcrystalline glass is CaO-MgO-BaO-SiO 2 Is a glass ceramic.
In some embodiments, the SiO 2 Is crystalline SiO 2 The purity is more than 99.5 percent, and the granularity is 1-2 mu m.
In some embodiments, the modifier is Bi 2 O 3 The purity is more than 99.5 percent.
In addition, the invention also discloses a preparation method of the low-dielectric high-temperature-stability LTCC material, which comprises the following steps:
1) Taking a part of microcrystalline glass and b parts of Al in percentage by mass 2 O 3 Ceramic powder, c part of SiO 2 Ceramic powder, d parts of CaTiO 3 Ceramic powder and e parts of modifier; wherein a is 55-60%, b is 20-25%, c is 10-15%, d is 8-12%, e is 1-3%, and a + b + c + d + e =100%;
2) Ball-milling the ingredients in the step 1), uniformly mixing, and drying;
3) Adding a bonding agent for granulation, pressing and forming, and then sintering in an air atmosphere at 880-895 ℃ to obtain the LTCC material with low dielectric and high temperature stability.
In some embodiments, in the step 2), water is used as a solvent, the ingredients are subjected to planetary ball milling for 3-6 h, and the particle size of the slurry is controlled by D 50 0.5-2 μm; the binder is a polyvinyl alcohol PVA binder.
In some embodiments, in step 3), a glue removing operation is further performed after the press forming and before the sintering.
In some embodiments, the temperature of the glue discharging operation is 450-500 ℃.
In some embodiments, the step 1) comprises adding a titanium oxide to the mixture 3 The ceramic powder is prepared by the following preparation method, including: according to CaCO 3 ：TiO 2 Is 1:1, adding zirconia balls and water, and mixing by a planetary ball mill; drying, crushing, sieving, calcining at 1100-1150 deg.c for 2-4 hr, ball milling to obtain CaTiO powder of 0.5-2 micron size 3 And (3) ceramic powder.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a glass ceramic composite system, and microcrystalline glass and Al with specific contents are adopted 2 O 3 Ceramic powder, siO 2 Ceramic powder and CaTiO 3 The ceramic powder is compounded, the prepared low-dielectric high-temperature-stability LTCC material can be sintered and compacted below 900 ℃, the dielectric constant is 7.8-8.2, the dielectric loss is less than 1 per thousand, the frequency temperature coefficient is-5 to +5 ppm/DEG C, the bending strength is more than 250MPa, the material has low dielectric constant and dielectric loss, and simultaneously has a near-zero frequency temperature coefficient (-5 to +5 ppm/DEG C), the stability and reliability of devices are facilitated, and the low-dielectric high-temperature-stability LTCC material can be applied to devices of an LTCC process.
Drawings
FIG. 1 is a flow chart of the steps of a method for preparing a low dielectric high temperature stability LTCC material according to an embodiment of the invention;
FIG. 2 is a micro-topography of a sintered sample of a low dielectric high temperature stability LTCC material prepared in example 3 of the present invention;
fig. 3 is a micro-topography of sintered samples of the dielectric material prepared in prior art comparative example 1.
Detailed Description
The invention will be further described with reference to the accompanying drawings and preferred embodiments. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
It should be noted that the terms of orientation such as left, right, upper, lower, top and bottom in the present embodiment are only relative concepts or are referred to the normal use status of the product, and should not be considered as limiting.
Aiming at solving the problem of CaO-MgO-SiO in the prior art 2 Is microcrystalline glass and Al 2 O 3 The problem of large frequency temperature coefficient of the ceramic composite material. The embodiment of the invention provides a low-dielectric high-temperature-stability LTCC dielectric material and a preparation method thereof, which are used for realizing a dielectric material which is sintered and compact at 880-895 ℃, has a dielectric constant of 7.8-8.2, dielectric loss of less than 1 thousandth, a frequency temperature coefficient of-5 to +5 ppm/DEG C and bending strength of more than 250 MPa.
In order to achieve the purpose, the embodiment of the invention adopts the following technical scheme: the LTCC material with low dielectric constant and high temperature stability is a glass ceramic composite material comprising microcrystalline glass in a weight proportion and Al in b weight proportion 2 O 3 Ceramic powder, c part of SiO 2 Ceramic powder, d parts of CaTiO 3 Ceramic powder and e parts of modifier. Wherein a is 55-60%, b is 20-25%, c is 10-15%, d is 8-12%, e is 1-3%, and a + b + c + d + e =100%.
In the embodiment of the invention, the microcrystalline glass is CaO-MgO-BaO-SiO 2 Is a glass ceramic.
SiO in the examples of the present invention 2 Is crystalline SiO 2 The purity is more than 99.5 percent, and the granularity is 1-2 mu m.
In the embodiment of the invention, the modifier is Bi 2 O 3 The purity is more than 99.5 percent.
The composite material system is composed of CaO-MgO-BaO-SiO 2 Microcrystalline glass, al 2 O 3 Ceramic phase, caTiO 3 Ceramic phase, siO 2 Ceramic phase, modifier Bi 2 O 3 And (4) forming. Wherein CaO-MgO-BaO-SiO 2 On one hand, the microcrystalline glass is the key for realizing low-temperature sintering of the composite material, and on the other hand, the microcrystalline glass is CaO-MgO-BaO-SiO 2 The microcrystalline glass can separate out CaMgSi 2 O 6 Phase of CaMgSi 2 O 6 Phase, al 2 O 3 Ceramic phase, caTiO 3 Ceramic phase, siO 2 The ceramics will influence the composition togetherDielectric constant and dielectric loss of the material. In addition, caTiO 3 The ceramic phase is also key to the improvement of the frequency temperature coefficient of the composite material.
Modifier Bi 2 O 3 And CaO-MgO-BaO-SiO 2 The microcrystalline glass plays a synergistic role and promotes the densification of sintering together. It should be noted that, for the composite material of the glass ceramic system, the composition, content and distribution of each phase, the softening temperature and crystallization temperature of the glass-ceramic, the wetting effect between the glass-ceramic phases and the sintering compactness of the glass-ceramic all affect the final properties. Specifically, caO-MgO-BaO-SiO 2 Content of microcrystalline glass, al 2 O 3 Content of ceramic phase, caTiO 3 Ceramic phase content, siO 2 Content of ceramic phase, modifier Bi 2 O 3 Content of CaO-MgO-BaO-SiO 2 The crystallization degree of the microcrystalline glass in the sintering process, and the wettability and compatibility between the glass phase and the ceramic phase have great influence on the performance.
The embodiment of the invention also provides a preparation method of the LTCC material with low dielectric constant and high temperature stability, which comprises the following steps:
1) Taking a part of microcrystalline glass and b part of Al in parts by mass 2 O 3 Ceramic powder, c part of SiO 2 Ceramic powder, d parts of CaTiO 3 Ceramic powder and e parts of modifier. Wherein a is 55-60%, b is 20-25%, c is 10-15%, d is 8-12%, e is 1-3%, and a + b + c + d + e =100%;
2) Ball-milling the ingredients in the step 1), uniformly mixing, and drying;
3) Pressing the mixture particles, removing the glue, and sintering in an air atmosphere at 880-895 ℃ to obtain the LTCC material with low dielectric and high temperature stability.
In the step 2), water is used as a solvent, the ingredients are subjected to planetary ball milling for 3-6 h, and the granularity of the slurry is controlled by D 50 0.5-2 μm; the binder is a PVA binder.
In the step 3), the glue discharging operation is also carried out after the compression molding and before the sintering.
The temperature of the rubber discharging operation is 450-500 ℃.
The CaTiO 3 The ceramic powder is prepared by the following preparation method, including: according to CaCO 3 ：TiO 2 Is 1:1, weighing and mixing, preferably adding zirconia balls and water, and mixing by a planetary ball mill; drying, crushing, sieving, calcining at 1100-1150 deg.c for 2-4 hr, ball milling to obtain CaTiO powder of 0.5-2 micron size 3 And (3) ceramic powder.
The schematic flow chart of the preparation method of the embodiment of the invention is shown in fig. 1, and comprises the following steps:
s1, according to CaCO 3 ：TiO 2 Is 1:1, calcining for 2-4 h at 1100-1150 ℃, and then ball-milling to obtain CaTiO 3 And (3) ceramic powder.
S2, caO-MgO-BaO-SiO in an amount of 55 to 60 percent 2 Glass, 20-25% of Al 2 O 3 Ceramic powder, 8-12% of CaTiO 3 Ceramic powder, 10-15% SiO 2 Ceramic powder and 1-3% of modifier.
S3, ball-milling and mixing the ingredients, D 50 The granularity is controlled to be 0.5-2 mu m, and then the mixture is dried.
And S4, adding an adhesive to granulate, performing compression molding, performing binder removal, and sintering in an air atmosphere at 880-895 ℃ to obtain the low-dielectric high-temperature-stability LTCC material.
Example 1
A low-dielectric high-temperature-stability LTCC material and a preparation method thereof are carried out according to the following steps:
1)CaTiO 3 preparing ceramic powder: the material is mixed according to the following components: according to CaCO 3 ：TiO 2 Is 1:1, weighing and mixing, preferably adding zirconia balls and water, and mixing by a planetary ball mill; drying, crushing, sieving, calcining at 1100 deg.C for 4 hr, and ball milling to obtain CaTiO powder with particle size of 2 μm 3 Ceramic powder;
2) Weighing 55 percent of microcrystalline glass and 25 percent of Al by mass fraction 2 O 3 Ceramic powder, 10% SiO 2 Ceramic powder, 8% CaTiO 3 Ceramic powder, 2% Bi 2 O 3 Mixing the raw materialsPlanetary ball milling for 3h, particle size control D 50 2.0 μm, and then drying;
3) Adding PVA adhesive for granulation, pressing and molding, discharging glue at 450 ℃, and then sintering in air atmosphere at 880 ℃ to obtain LTCC dielectric material with low dielectric constant and high temperature stability;
4) The dielectric property of the cylindrical sintered body is tested by a resonant cavity method, the three-point bending strength of the strip-shaped sample after sintering is tested by a universal mechanical tester, and the performance results are detailed in table 1.
Example 2
A low-dielectric high-temperature-stability LTCC material and a preparation method thereof are carried out according to the following steps:
1)CaTiO 3 preparing ceramic powder: the material is mixed according to the following components: according to CaCO 3 ：TiO 2 Is 1:1, weighing and mixing, preferably adding zirconia balls and water, and mixing by a planetary ball mill; drying, crushing, sieving, calcining at 1100 deg.C for 4 hr, and ball milling to obtain 2 μm CaTiO 3 Ceramic powder;
2) Weighing 55 percent of microcrystalline glass and 20 percent of Al by mass fraction 2 O 3 Ceramic powder, 11% SiO 2 Ceramic powder, 12% CaTiO 3 Ceramic powder, 2% Bi 2 O 3 Mixing, ball milling for 3 hr, and controlling granularity D 50 2.0 μm, and then drying;
3) Adding PVA adhesive for granulation, pressing and molding, discharging glue at 450 ℃, and then sintering in air atmosphere at 880 ℃ to obtain LTCC dielectric material with low dielectric constant and high temperature stability;
4) The dielectric property of the cylindrical sintered body is tested by a resonant cavity method, the three-point bending strength of the strip-shaped sample after sintering is tested by a universal mechanical tester, and the performance results are detailed in table 1.
Example 3
A low-dielectric high-temperature-stability LTCC material and a preparation method thereof are carried out according to the following steps:
1)CaTiO 3 preparing ceramic powder: the components are mixed as follows: according to CaCO 3 ：TiO 2 Is 1:1, preferably by adding an oxidizing agentMixing zirconium balls and water by a planetary ball mill; drying, crushing, sieving, calcining at 1100 deg.C for 4 hr, and ball milling to obtain CaTiO powder with particle size of 2 μm 3 Ceramic powder;
2) Weighing 55 percent of microcrystalline glass and 20 percent of Al by mass fraction 2 O 3 Ceramic powder, 12% SiO 2 Ceramic powder, 10% CaTiO 3 Ceramic powder, 3% Bi 2 O 3 Mixing, ball milling for 6 hr, and controlling granularity D 50 Is 1.0 mu m and then is dried;
3) Adding PVA adhesive for granulation, pressing and molding, discharging glue at 450 ℃, and then sintering in air atmosphere at 895 ℃ to obtain LTCC dielectric material with low dielectric constant and high temperature stability;
4) The dielectric property of the cylindrical sintered body is tested by a resonant cavity method, the three-point bending strength of the strip-shaped sample after sintering is tested by a universal mechanical tester, and the performance results are detailed in table 1.
Fig. 2 is a micro-topography diagram of a sample of the low-dielectric high-temperature-stability LTCC dielectric material prepared in example 3 after being sintered in an air atmosphere at 895 ℃, and it can be seen from the figure that the prepared low-dielectric high-temperature-stability material has good compactness.
Example 4
A low-dielectric high-temperature-stability LTCC material and a preparation method thereof are carried out according to the following steps:
1)CaTiO 3 preparing ceramic powder: the components are mixed as follows: according to CaCO 3 ：TiO 2 Is 1:1, weighing and mixing, preferably adding zirconia balls and water, and mixing by a planetary ball mill; drying, crushing, sieving, calcining at 1100 deg.C for 4 hr, and ball milling to obtain CaTiO powder with particle size of 2 μm 3 Ceramic powder;
2) Weighing 55 percent of microcrystalline glass and 20 percent of Al by mass fraction 2 O 3 Ceramic powder, 15% SiO 2 Ceramic powder, 8% CaTiO 3 Ceramic powder, 2% Bi 2 O 3 Mixing, ball milling for 6 hr, and controlling granularity D 50 Is 1.0 mu m and then is dried;
3) Adding PVA adhesive for granulation, performing compression molding, discharging glue at 450 ℃, and sintering in an air atmosphere at 895 ℃ to obtain the LTCC dielectric material with low dielectric and high temperature stability;
4) The dielectric property of the cylindrical sintered body is tested by a resonant cavity method, the three-point bending strength of the strip-shaped sample after sintering is tested by a universal mechanical tester, and the performance results are detailed in table 1.
Example 5
A low-dielectric high-temperature-stability LTCC material and a preparation method thereof are carried out according to the following steps:
1)CaTiO 3 preparing ceramic powder: the components are mixed as follows: according to CaCO 3 ：TiO 2 Is 1:1, weighing and mixing, preferably adding zirconia balls and water, and mixing by a planetary ball mill; drying, crushing, sieving, calcining at 1100 deg.C for 4 hr, and ball milling to obtain CaTiO powder with particle size of 2 μm 3 Ceramic powder;
2) Weighing 60 percent of microcrystalline glass and 20 percent of Al by mass fraction 2 O 3 Ceramic powder, 10% SiO 2 Ceramic powder, 9% CaTiO 3 Ceramic powder, 1% Bi 2 O 3 Mixing, ball milling for 6 hr, and controlling granularity D 50 Is 1.0 mu m and then is dried;
3) Adding PVA adhesive for granulation, performing compression molding, discharging glue at 450 ℃, and sintering in an air atmosphere at 895 ℃ to obtain the LTCC dielectric material with low dielectric and high temperature stability;
4) The dielectric property of the cylindrical sintered body is tested by a resonant cavity method, the three-point bending strength of the strip-shaped sample after sintering is tested by a universal mechanical tester, and the performance results are detailed in table 1.
Comparative example 1
The difference between the comparative example 1 and the example 1 is whether a modifier Bi is added into the material proportion 2 O 3 Comparative example 1 in terms of mass fraction, 55% of microcrystalline glass and 25% of Al were weighed 2 O 3 Ceramic powder, 10% SiO 2 Ceramic powder, 10% CaTiO 3 The ceramics are proportioned and are subjected to planetary ball milling for 3 hours, and the granularity is controlled by D 50 2.0 μm, oven drying, adding PVA, granulating, press molding, removing gel at 450 deg.C, and mixingSintering at 880 ℃ in an air atmosphere to obtain a sintered sample.
FIG. 3 is a cross-sectional micro-topography of the sintered sample of comparative example 1, and it can be seen that comparative example 1 has no modifier Bi added 2 O 3 Under the condition of (3), the sample has more holes in the micro-morphology and poor compactness. The results of the properties shown in Table 1 show that the increase of the extrinsic loss, the deterioration of the dielectric properties and the reduction of the bending strength are also evident due to the poor sintering compactness. It can also be seen from the combination of comparative example 1 and the examples that the microcrystalline glass and the modifier Bi are added by the modifier 2 O 3 Can generate synergistic action, is more beneficial to the compactness of sintering, thereby improving the performance.
Comparative example 2
Comparative example 2 is CaO-MgO-SiO 2 Is microcrystalline glass and Al 2 O 3 Compounding, namely weighing 60 percent of microcrystalline glass and 40 percent of Al by weight percent of the comparative example 2 in the comparison group without adding other ceramic phases and modifiers 2 O 3 Ceramic powder is mixed and is subjected to planetary ball milling for 3 hours, and the granularity is controlled by D 50 2.0 μm, then drying, adding PVA adhesive for granulation, pressing and molding, discharging glue at 450 ℃, and then sintering in air atmosphere at 880 ℃ to obtain a sintered sample. As can be seen from the results of the properties shown in Table 1, caO-MgO-SiO in comparative example 2 2 Is microcrystalline glass and Al 2 O 3 The composite material is also a low dielectric and low loss material, the dielectric constant of the composite material is about 8.3, the dielectric loss is about 1 thousandth, but the frequency temperature coefficient of the composite material is particularly large, and the frequency temperature coefficient is about-45 ppm/DEG C, so that the composite material is limited to be applied in a scene with high requirement on temperature stability. In contrast, in examples 1 to 5, the dielectric constant and the dielectric loss are relatively close to those of comparative example 2, but the temperature coefficient of frequency is significantly improved, and the temperature coefficient of frequency of examples 1 to 5 is between-5 to +5 ppm/DEG C, which is significantly superior to that of comparative example 2. The bending strength is slightly reduced, but still has the bending strength more than 260MPa, and can completely meet the requirements of most LTCC devices.
TABLE 1
As shown in the table 1, the material components, dielectric properties, frequency temperature coefficients, bending strength and other properties of the materials of the examples 1-5 and the comparative examples 1-2 are given, and the comparison of the results in the table 1 shows that the materials of the examples 1-5 can be sintered and compacted at 880-895 ℃ and can be co-sintered with Ag paste at low temperature; the dielectric constant is in the range of 7.8-8.2, the dielectric loss is less than 1 thousandth, the frequency temperature coefficient is-5- +5 ppm/DEG C, the bending strength is more than 260MPa, and the material can be used as a low-dielectric low-loss high-temperature stability material and can be applied to filters, couplers, substrates and other devices in an LTCC process.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several equivalent substitutions or obvious modifications can be made without departing from the spirit of the invention, and all the properties or uses are considered to be within the scope of the invention.
Claims (9)
1. The LTCC material with low dielectric and high temperature stability is characterized by adopting a glass ceramic complex material and comprising a parts of microcrystalline glass and b parts of Al in mass fraction 2 O 3 Ceramic powder, c part of SiO 2 Ceramic powder, d parts of CaTiO 3 Ceramic powder and e parts of modifier; wherein a is 55 to 60%, b is 20 to 25%, c is 10 to 15%, d is 8 to 12%, e is 1 to 3%, and a + b + c + d + e =100%.
2. The low dielectric high temperature stability LTCC material of claim 1, wherein the glass-ceramic is CaO-MgO-BaO-SiO 2 Is a glass ceramic.
3. The low dielectric high temperature stability LTCC material of claim 1, wherein the SiO is 2 Is crystalline SiO 2 The purity is more than 99.5 percent, and the granularity is 1-2 mu m.
4. The low dielectric high temperature stability LTCC material of claim 1, wherein the modifier is Bi 2 O 3 The purity is more than 99.5 percent.
5. A preparation method of a low-dielectric high-temperature-stability LTCC material is characterized by comprising the following steps:
1) Taking a part of microcrystalline glass and b parts of Al in percentage by mass 2 O 3 Ceramic powder, c parts of SiO 2 Ceramic powder, d parts of CaTiO 3 Ceramic powder and e parts of modifier; wherein a is 55-60%, b is 20-25%, c is 10-15%, d is 8-12%, e is 1-3%, and a + b + c + d + e =100%;
2) Ball-milling the ingredients in the step 1), uniformly mixing and drying;
3) Adding a bonding agent for granulation, pressing and forming, and then sintering in an air atmosphere at 880-895 ℃ to obtain the LTCC material with low dielectric and high temperature stability.
6. The method for preparing the low dielectric high temperature stability LTCC material as claimed in claim 5, wherein in the step 2), the ingredients are subject to planetary ball milling for 3-6 h by using water as a solvent, and the particle size of the slurry is controlled by D 50 0.5-2 μm; the binder is a polyvinyl alcohol PVA binder.
7. The method for preparing the low dielectric constant, high temperature stability LTCC material of claim 5, wherein in the step 3), a binder removal operation is further performed after the compression molding and before the sintering.
8. The method for preparing the low dielectric high temperature stability LTCC material of claim 7, wherein the temperature of the binder removal operation is 450-500 ℃.
9. The method for preparing the low dielectric high temperature stability LTCC material of any one of claims 5-8, wherein in the step 1), caTiO 3 The ceramic powder is prepared by the following preparation methodThe method comprises the following steps: according to CaCO 3 ：TiO 2 Is 1:1, adding zirconia balls and water, and mixing by a planetary ball mill; drying, crushing, sieving, calcining at 1100-1150 deg.c for 2-4 hr, ball milling to obtain CaTiO powder of 0.5-2 micron size 3 And (3) ceramic powder.
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